Production of zirconium and hafnium oxides in a fluidized bed



July l0, 1962 w. HUGHES ETAL 3,043,656

PRODUCTION OF' ZIRCONIUNI AND HAFNIUNI OX'IDES IN A FLUIDIZED BED Filed Feb. 19, 1962 5 Sheets-Sheet 1 ,4 fraz/vigas July l0, 1962 w. HUGHES ETAL 3,043,655

PRODUCTION oF zRcoNm/l AND HAFNIUM OXIDES 1N A FLUIDIZED 'BED Filed Feb. 19, 1962 5 SheetS-Sheeb 2 l /A/vf/vra/zs wrm/AM Hua-Hasn mama/z WALL/cf avm:

July 10, 1962 w. HUGHES ETAL PRODUCTION OF' ZIRCONIUM AND HAFNIUIV] OXIDES IN A FLUIDIZED BED 5 Sheets-Sheet 3 Filed Feb. 19, 1962 ArroRA/M July 10, 1962 w. HUGHES ETAL. 3,043,656

PRODUCTION oF ZIRCONIUM AND HAFNIUM OXIDES IN A FLUIDIZED BED 5 Sheets-Sheet 4 Filed Feb. 19, .w62

l/VVE/VORS -W/L/HM HUG/'MTM ARTHUR WALLACE EVA/VS .BY 5a/cama ATTUMIXS July l0, 1962 Filed Feb. 19, 1962 W. vHUGHES ETAL PRODUCTION oF zIRcoNuII/I AND HAFNIUII/I oxIDEs IN A FLUIDIZED BED 5 sheets-sheet 5 AIR IOZ

(N07 Wouw/- SAND C12 ABSORRTION E COOLING II FEED I 35 SEPARATION C 2 CI I' Zr 52" A or Z AIR y ,J2 "@5532 REACTION Y PURIFIER A+ A* II AIR& 0 Z 0 7 9 2 H222 l MOISTURE r 02 Hf 02 AIR SAND L /@8 wf/vrees United States Patent O 3,043,656 PRODUCTION F ZHRCONUM AND HAFNIUM XIDES IN A FLUIDZED BED William Hughes, Faireld, Stockton-ou-Tees, and Arthur Wallace Evans, Nunthorpe, Middlesbrough, England, assignors to British Titan Products Company Limited, Durham, England, a company of the United Kingdom Filed Feb. 19, 1962, Ser. No. 173,88) Claims priority, application Great Britain Aug. 6, 1953 17 Claims. (Cl. 23a-140) This invention is for improvements in or relating to the preparation of metallic oxides, more particularly the oxides of zirconium and hafnium having halides which exist in vapor form at temperatures below 350 C. at atmospheric pressure. Particular examples of such metallic oxides producible in accordance with the present invention are zirconium dioxide and hafnium dioxide.

This present application is a continuation-impart of application Serial No. 447,648, tiled August 3, 1954, entitled Preparation of Titanium Dioxide, now Patent No. 2,828,187, dated March 25, 1958, a continuation-impart of application Serial No. 720,470, tiled March 10, 1958, entitled Production of Silicon Dioxide, a continuationin-part of application Serial No. 721,578, filed March 14, 1958, entitled Preparation of Titanium Dioxide, now abandoned, a continuation-in-part of application Serial No. 721,579, tiled March 14, 1958, entitled Production of Metal Oxides, and a continuation-in-part of application Serial No. 739,418, filed June 2, 1958, for Production of Silicon Dioxide.

The co-pending application Serial No. 721,579 discloses and claims the production of oxides from halides of titanium, silicon and aluminium. The present application discloses and claims the production of oxides from halides of zirconium and hafnium by the use of a process similar to that disclosed and claimed in application Serial No. 721,579 with reference to halides of titanium, silicon and aluminium.

Processes for the production of iinely divided oxides have been suggested in which the corresponding Vaporized halide, particularly the chloride, is converted to the oxide by various procedures involving oxidation or hydrolysis at elevated temperatures.

These processes, though varying considerably in detail, all require the use of burners or jet assemblies for feeding the reactantgases and vapors to the reaction space. The apparatus is often further complicated by the need to maintain the reaction temperature and, in some cases, to provide the moisture for the hydrolysis reaction by the simultaneous combustion of hydrogen, hydrocarbons or other vaporized fuels. In these processes it is rarely possible to increase the production of the apparatus by an increase in the size of the jets or burners as this usually leads to a deterioration in the quality of the product. Consequently, for large scaleV production itis necessary to use a large number of similar jets or burners.

It is an object of the present invention to provide a process for the manufacture of oxides of zirconium and hafnium as aforesaid which is highly eiiicient and in which the reaction temperature can be readily controlled, and which is more adaptable for large scale operation.

It is a further object of the invention to provide a process for the manufacture of oxidesV of zirconium and hafnium `as aforesaid from the corresponding halides, particularly the corresponding chlorides, which o-bviates or minimizes the disadvantages of prior art processes.

A still further object of the invention is the production o-f oxides of zirconium and hafnium as aforesaid by continuous methods utilizing uidized beds carried out in large scale reactors under self-sustaining conditions where no heat need be supplied to maintain the reaction, Vi.e. the action being carried out under autothermal conditions.

lOther objects include the utilization of reaction conditions acording to which the gaseous and vaporized reactants are delivered to the reaction zone under conditions ensuring maintained uniform conditions while the relative proportions of the reactants are controlled as desired.

Still further objects and advantages will appear from the more detailed description given below, it being understood that such more detailed disclosure is given by way of explanation and illustration only and not by way of limi-tation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

It has been shown in the parentap-plication Serial No'. 721,579 that metal halides may be oxidized by establishing a uidized bed of inert solid particulate material, maintaining the temperature of said bed sufficiently high to cause the metal halide to react with oxygen While introducing the metal halide and oxygen into said bed, whereby the metal oxide is formed, and carrying the metal oxide thus produced laway with the gases leaving the fluidized bed.

The particulate inert solid material constituting the bed in which the reaction is to take place may be selected from sand-like materials, i.e. silica, Zircon, mineral rutile, alumina or massive mineral rock materials which are resistant to chlorine or chlorine-containing substances likely to be present in the course of the oxidation reaction described and at the temperatures encountered, and may, if necessary, have been treated with chlorine at high ternperatures in order to remove any undesirable impurities which might otherwise be attacked during the oxidation reaction and thereby contaminate the product. The sandlike material is preferably substantially entirely composed of particles not less than 76 microns in dia-meter and normally not greater than about one-eighth of an inch in size. The particle size of material should, in any case, be not less than 40p, preferably 80u, and not substantially greater than 1000;:4 diameter. By carefully `grading the bed material in respect of the sizes of the particles thereof it is possible to control, Within limits, the progress of the reaction within the bed.

Zircon sand with a mean particle size of is the substrate material of choice. It will be appreciated that the term massive mineral relates to minerals which are of such compact nature that the density of each particle thereof approximates the density of a substantially perfect specimen of the material. The material comprising the fluidized bed should be such that it would iluidize in an air stream at a temperature of 1000 C. for 100 hours at a velocity live times the minimum fluidizing velocity, and the amount of dust and iine material carried away in suspension in the emerging `air stream would not exceed 5 percent (preferably one percent or below) of the material originally present in the bed. The metal halides react with oxygen within the bed to form the appropriate metal oxide and halogen. lFor instance zirconium tetrachloride reacts with oxygen according to the following equation:

Hafniurn tetrachloride reacts with' oxygen according to the following equation:

HfCl4-l-O2=HfO2-{2Cl2 valent metals is preferably within the range 1:1 to 2:1.

epesses Higher proportions of oxygen, e.g. up to 5:1, may be used, but complete reaction of the metal halide is generally achieved within thek preferred range. Molar ranges less than 1:1 obviously give incompleteroxidation of the halides of tetravalent metals.

The reactants may be used in a relatively dry condition, or, for control in the reaction, a little moisture may be tolerated, particularly in the oxygen stream. It will be appreciated that the presence of more than a little moisture is desirably to be avoided, since, for instance when the halide starting material is a chloride, .the presence of moisture may convert the chlorine produced to hydrochloric acid. The latter is generallydetrimental to the process, in that hydrochloric acid cannot so readily be reused for the purpose of chlorination, as normally conducted in accordance with the preferred process of this invention. On the other hand, the chlorine produced can conveniently be utilized for theproduction `of further supplies of metal halides by `chlorination of metalliferous materials, but preferably in the absence of acidic gases such as hydrogen chloride.

The temperature of the iluidized bed for oxidation should be maintained within the range of 500 C. to l300 C., preferably 900 C, to 1100v C., the range of 1000" C. to l050 C. giving especially goo-d results. The reaction is exotherrnic and the bed of'solid inert particles acts as a heat reservoir. With -a well-insulated furnace, the heat generated by the reaction may suce to maintain the reaction without supplying auxiliary heat. However, in the case of small installations, it is generally required that additional heat should be applied, for instance by external heating means, by admitting one `or both reactants into the bed in a heated state, or by admitting a combustible gas to 4the bed so as to burn with gaseous oxygen and supply the required additional heat.

However, when it is desired to carry out the operation on a large scale, the use of external heating should be avoided since, owing to the corrosive nature of the metal halides and of the reaction products, the furnace is likely to be constructed of ceramic non-conductive material, and so external heating is not only uneconornic but is also ditlicult to control in the'sense that the temperature conditions over a large reactor tend to be irregular, and this brings about variations in the product. An'important advantage of the present invention is that it makes possible the autothermal oxidation of metal halides on a large scale and so avoids the necessity of external heating, and the consequent variations in the product.

As has been indicated above, it is important to minimize variations in the product, andl it is in consequence desirable to distribute the reactant gases uniformly over the cross-section of the reactor furnace. This lproblem is not of such great importance in small-scale reactors. With large-scale reactors, the problem arises of obtaining uniform conditions of fluidization and proper intermingling and distribution of the reactants and the present invention solves thisproblem with respect to the production of zirconium dioxide and hafnium dioxide.

A particularly advantageous method of operation comprises reacting the vapor of lthe metal halide with oxygen cpg. elemental or free oxygen in the course of their upward passage throughv a fluidized bed of inert solid material so that the metal oxide which is produced is at least for the most partdischarged from above the bed entrained in outgoing gases, characterized by the following features: Y n

(a) That the reactantsr Iare heated in the bed to the extent required tocause them to react so that external preheating is not required; y

(b) That the bed, adequately insulated, containsV a suicient quantity ofthe inert solid material to conserve from the heat of the exothermic reaction what is necessary to effect continuously said heating of the reactants which are, or at leastone of which is, being introduced so rapidly as to fluidize the bed in the desired manner;

(c) That the reactants are introduced into the bed through a plurality of inlet ducts distributed and mutually arranged with respect to the horizontal .cross-sectional area of the bed so as to enable uniform fluidization of the bed. The reactants may be pre-mixed but it is preferred to introduce them separately into the bed through respective inlet ducts distributed and arranged as aforesaid and so as to ensure the intermingling of the respective reactants required for their interreaction to take place within the bed;

(d) That the inlet ducts for the reactants are provided with constrictions of predetermined dimensions to ensure that a supply under pressure of the reactants, in their required proportions, is appropriately distributed `among the inlet ducts appertaining thereto; and

(e) That each constriction in an inlet duct produces a pressure drop from the pressure of the supply of reactant thereto which is at least one half of the pressure drop from the bottom to the top of the fluidized bed.

As regards (a) above it will be understood that external preheating of the reactants is not icomplete-ly precluded because, in the rst place, the metal halide will Abe preheated at least to the extent of vaporizing it and, in the second place, there is no disadvantage, if convenient to do so, to use oxygen which is preheated toa moderately raised temperature, e.g. -to 50 to 250 C. Where the `oxygen and metal halide are pre-mixed, it is desir-able to preheat the oxygen lat least tot the extent necessary to prevent condensation of the metal halide vapor, e.g. up to 400 C., the precise temperature depending on the particular metal halide used.

As regards (b) above it is obvious that the sizeof the cross-sectional area of the bed is a more important factor than height of the bed Ybecause increase of height to Iaccommodate the required amount of bed material would unduly increase heat losses apart from requiring larger iluidzing forces. Therefore, to achieve the desired autothermal operation of the process there is a minimum size for the cross-sectional area of the bed `and we estimate that this means, assuming a cylindrical reaction chamber, that the diameter of the bed must be at least fteen inches. It may of course be larger but it should be borne in mind, that in designing for substantially larger diameters, the conserved heat may exceed what is required to maintain the reaction and that provision for cooling of the reaction zone should therefore -be made.

The fluidized bed employed may be as described hereinbefore as to bed materials, particle size, and like details, except that, as has already 'been specified, there should be sufficient inert solid material to conserve from the heat of the exothermic reaction at least what is necessary to maintain continuance of the reaction.

As has already been mentioned, the gaseous reactants are continuously introduced into the inert hot bed through a plurality of inlet ducts to maintain uniformity of reaction throughout the bed. The velocity of the gas maintaining the bed in the fluidized state is desirably between two andfty times the minimum required for liuidization, and preferably between three and ten times such minimum. For this purpose, the inlet ducts are provided with the above-mentioned constrictions, the size of which is so chosen that with the necessary rate of gas-flow the pressure-drop across :the constrictions is at least one half, and desirably less than fty times, thepressure-drop of the gas in passing through the bed, thus affording a substantially even flow of the gaseous reactants over the whole of the bed material.

' ameter considerably greater than fifteen inches (say eighteen inches or greater) may be controlled, in the sense 'of being kept down as necessary, by the use'of gaseous coolants as exemplified by chlorine, nitrogen, carbon dioxide or cooled recycled t-aii gases which may be introduced directly into the iluidized bed, or by liquid chlorine injected into or sprayed upon the bed. In addition, or alternatively, the temperature of the reactor may be controlled by introducing, progressively, relatively cool sand or other inert bed material into the bed, Iand correspondingly discharging hot sand from the bed Under the temperature conditions hereinbefore specified, other general control factors may be varied to maintain the conditions desired. Thus the oxygen gas and metal halide vapor will usually be fed to the reactor `at a velocity (assuming the reactor to be empty) of from about one quarter to about two feet per second, or higher. Where-bed material is progressively fed into `and out of the reactor, the rate of feed may vary. But any conditions used should preferably be balanced for autothermal operation. In general, it may be noted that in any given installation the insulation is fixed, and the oxygen and meta-l halide feed is determined at least in part by the -amounts required to maintain fluidization. Under these Vcircumstances the temperature will usually be kept down within the desired range by feed of extraneous coolant or of bed material as mentioned above.

In a preferred embodiment, the reactor is essentially a vertical shaft, usually cylindrical, and lined internally with chlorine-resisting brickwork which, in turn, is protected by an outer shell of insulating brick, the whole being contained within a steel shell, the latter termin-ated at the 'top and the bottom with openings corresponding to the shaft on which are constructed extension pieces which are flanged to take -a header in the case of the top and a hearth unit to be attached to the bottom. The latter unit desirably consists of a steel plate, surmounted by a heat-insulating block sealed thereto and itself surmounting gas-inlet and `gas-supply means. The steel plate contains a number of apertures spaced uniformly according to a predetermined plan in order to provide 'for the admission of Ithe reactants, and the insulating block contains a number of bores, in which refractory tubes may be tted, to` provide passages registering with the `apertures. The apertures in the plate are fitted with gas-inlet means having constrictions of predetermined size. The passages through the insulating block may optionally be provided yat their upper ends with devices designed to prevent sol-ids from falling down therethrough but to permit the ow of gas upwards. Said block functions essentially to insulate from the heat of the reactor the metal plate and the gas-inlet means and gas-supply devices positioned below. The whole hearth unit assembly is constructed so as to tit into the base of the furnace shaft so that the metal plate supporting the structure may be attached to the lower flanged end of the steel shell of the furnace.

One set of the inlet means is designed for the admission of metal halide and another set, appropriately neighbored with the rst mentioned set, for the admission of the oxygen. The inlet means for metal halide into the appropriate passages may be connected to one or more manifolds or toa windbox, and the inlet means feeding the oxygen may similarly be connected to a separate manifold, or manifolds, `or windbox. In either case, it will be clear that the gas-inlet means, preferably welded onto or into the metal plate, will be of such length and so fabricated that they may be conveniently connected to link withl the respective manifolds or windboxes. With a Windbox construction, there may be a plug containing the above-mentioned constriction at the point of entry to each inlet means. In the case where a manifold is used, e'ach inlet means may comprise a pipe with -a flanged end connected with a corresponding flanged end of a pipe leading from the manifold, the constriction being present as an orifice in a disc held between the two flanged ends.

A preferred feature is that there should be an admission of the oxygen reactant round the walls of the reactor,

so far as possible, in order to avoid undue reaction at the static surface provided by the wall, as opposed to the dynamic surface provided by the uidized particles.

Although it is desirable to incorporate as large as possible a number of gas ports into the base of the reactor, there should not be so many ports as will weaken the base of the reactor. It is also of course desirable to makethe hearth unit `at the base of the reactor as insulating as possible so as to retain the heat of reaction within the furnace.

An essential feature according to this preferred and particularly advantageous method of operating the invention is the use of constrictions of predetermined dimensions in the inlet ducts for the reactants. These constrictions are an important controlling factor in the system of gas distribution, and the dimensions are determined having regard to the fluidization required, the properties, Le., the density and viscosity, of the reactant gas, and the amount of gas which it is desired to admit taking into account the number of inlet ducts available. It will be appreciated that the constrictions for the different reactants may be of different dimensions.

The header plate which is secured to the flanged end at the top of the steel shell of the furnace may |be constructed with tiwo openings, one for the temporary insertion of a poker or other suitable device to effect initial heating of the furnace and also for admission of the material lfor-ming the `bed, and the other for conveying the products of reaction from the furnace to suitable cooling,

Y collecting and/ or separating devices to be described hereinafter.

With the hearth unit aixed, any one of the abovementioned particulate solid inert materials, or a mixture of such materials, is fed into the furnace to a static depth desirably of approximately 1-3 feet. It may be more but this is usually unnecessary. The bed thus formed is then uidized by a stream of air fed through the inlets at the base of the reactor, and a pre-ignited gas poker may -be inserted into'the bed. In this Way, the furnace may be raised to a temperature of say approximately l C., whereupon the gas poker is removed, and the inlet through which it was injected suitably sealed. At this stage the air-stream is shut off and oxygen, or a gas rich in oxygen, is passed into the furnace through the appropriate inlets. The metal halide ductings, inlets and passages are, to start with swept with a stream of nitrogen, and then the metal halide is passed therethrough, -whereupon reaction takes place substantially entirely within the bed. The metal oxide thus produced is carried up out of the bed entrained ywith the chlorinecontaining product gases, and is desirably led from the furnace through the ducting in the header to suitable cooling, collecting and/or separating devices described later herein, which may be of various types.

The metal oX-ide produced by the reaction is in finelydivided state and is carried forward from the bed entrained as a suspension in the chlorine-containing product gases. The temperature of this mixture as it leaves the bed is in the neighborhood of 900-l200 C., normally varying within the range of SOO-1250 C. As the gases are corrosive it vbecomes necessary to effect cooling whilst they are still contained within apparatus lined with chlorine-resistant material until they are suiciently cooled ,to permit cooling in metal or other conduits which are more highly heat-conductive. Various methods of effecting this cooling may be used depending on the particular oxide concerned, such as lby quenching with wa- The gases which -7 uct gases, a small proportion of the` metal oxide may adhere tothe substrate material comprising the bed. Where the accumulation, after a period of time, becomes excessive, it may be necessary to discharge the bed completely and replace it, unless, as hereinbefore mentioned, the bed is progressively renovated.

In either case the metal oxide accretions on the bed material may, if desired, be removed by a separate procedure involving chlorination by methods which are themselves well-known in the art. Such material, after this cleansing and following appropriate cooling, may then be returned to the oxidation chamber for use in cooling and/ or renovating the bed. as mentioned above, and more fully described hereinafter. The accretion of metal oxidek on to the bed material should not be allowed to increase to such an extent that the iluidization of the bed is unduly hindered.

It has already been demonstrated that the heat evolved by the oxidation reaction is utilized to maintain the temperature and is adequate to do so. Thus the chamber should be well insulated and the rate of heatlost to the surroundings should not be greater than the rate at which the heat is evolved. It follows, therefore, that for the process to be autothermal, the reaction chamber will require to be adequately fabricated for this purpose, both in regard to size and materials of construction. As has already 4been stated, it has been found in practice when using well-known materials of construction, that a minimum internal diameter of a cylindrical shaft furnace is about inches. In employing a furnace of 15 inches in diameter it is possble to maintain the temperature by minor controls such as by slight variations in the rate of feed of the reactants. When however, furnaces of larger construction are employed, it is desirable, rather than to employ constructional material giving less insulation, to introduce into the bed cooling agents, as already indicated, whereby the temperature of reaction is kept down as required.

In a preferred embodiment, fully described hereinafter, cooling is effected and the temperature of reaction controlled yby continuously feeding cool solid inert iluidizable material to the bed t-o replace a corresponding amount of hot material which is continuously discharged. The amount of discharge and replacement will depend on the temperature of the replacement material at he time of feeding and the amount of heat to be removed. Thus to get the maximum heat removal with a minimum amount v of discharge and replacement, cold replacement material can be used. In the event, however, of it being desirable at the same time to increase thepurge in the bed, the replacement material may be fed in at an elevated temperature so as to obtain the same cooling effect with a larger feed and in consequence a greater purge. It will be appreciated that there may be two requirements (a) to cool the bed, and (b) to purge the bed, and by varying the temperature of the replacement material there is a freedom of action in respect of the quantity thereof to be admited. By such means, the bed may be progressively renovated, thusovercoming the possible drawback associated with accretion of metal oxide on the bed particles.

Preferred equipment which may be usedy for the invention is more particularly described with reference to the accompanying drawings, to some extent diagrammatic, y

in which:

FIGURE 1 -shows Vin vertical vsectional elevation a shaft Y furnace chamber, a solids-feeding device and a solids-collecting and cooling device;

FIGURE 7 is a diagrammatic sectional elevation of apparatus for separating products formed in the apparatus of FIGURE l; and

FIGURE 8V is a flow diagram illustrating the complete process operation as applied to the production of zirconium dioxide and, alternatively, hafnium dioxide by the oxidation of zirconium tetrachloride and hafnium tetrachloride respectively.

In FIGURE 1 there is shown by the general reference numeral 1 a furnace chamber lined with chlorine-resisting bricitwork 2 supported and lined on the outside with insulating brickwork 3, the whole being contained in a steel shell 5 which has openings at the top 6 and bottom 7,. On to these openings are welded short collars 8, terminating in flanges 9, the whole being mounted by means not shown, so that furnace 1 stands Ivertically.

A metal base plate 10 has surmounting it a ceramic block 11 constructed so that when the base plate 10` is inserted into the bottom opening 7 of the furnace 1, it will neatly tit whereby the block 11 serves to insulate from the shaft of the furnace 1 the base plate 10` below. rThe base plate contains apertures13 registering with bores 12 in the block 11, the apertures 13 and the bores 12| being distributed over the plate 10 and block 11 in a design which is shown in plan view in FIGURE 2.

In this particular and somewhat simplified design, the bores 12 are subdivided into (l) a set of passages 112 for admission of the metal halide, the passages 112 being arranged in the form of an Octagon, i.e. there being eight passages surrounding the centre of the block 11, and (2) a set of passages 212 and 312 for admission of oxygen, these latter passages being arranged in the form of an outer octagon of passages 212 and an additional passage 312 in the centre of the block 11, the apertures 13 registering with the passages 112, 212 and 312, as has already been indicated.

The upper parts of the bores in the ceramic block 11 may be fitted With gas-emergent means designed positively to bar ingress of the bed material, and yet to permit the passage of the reactant gases, but it is preferred to operate without the use of such devices, and have passages 12 of limited diameter such that the reactants may -be fed with sufficient velocity to prevent Vsolid Lbody material from falling `back into the passage. Thus FIGURE l shows passages 12 without any such devices.

FIGURE 1 shows an arrangementin which the passages 12 are fed with reactants from a manifold system. A similar system is also shown in more detail in FIG- URE 3, although in the latter figure, solids non-return devices in the form of porous caps are shown in the upper portions v15of the passages 12.

One manifold 25 distributes oxygen to passages 212 and 312, while another manifold 26 -distributes metal halide vapor to passages 112. All the passages 12 communicate with pipes 41 which are welded to the Vplate 10` and are tted with flanges 104 (see FIGURE 3) at their lower extremities. To each flange 104 is secured a vflange 105 on a pipe42 leading to the manifolds 25 and 26, respectively, for oxygen and metal halide, a constriction being provided by almachined orifice '47 present in a disc 43' being held between-the flanges 104 and 105.

FIGURE 3 also shows the provision of gas-permeable solids-impermeable devices 102, 202, and 302, in the upper portions of the passages 12, the latter being flared so as to accommodate the devices which prevent solids from falling into the passages and the gas-,feeding systems, while allowing the gas to escape therethrough; It will be seen that the devices 202' and 302 in the oxygen inlet passages 212 and 31,2, respectively, are of larger size than the devices-102 in the metal halide passages 112. Instead of these devices, other types may be used, but it is preferred to rely merely on the force of the iluidizing gases to prevent solid material from falling into the feed system.

A further modification is shown in FIGURES 5 and 6 where refractory tubes 401i made for example of an alumino silicate are tted in the bores in the insulating block 11, and have outlets to the furnace in their tops as shown at 410. Pipes 41 welded -to the plate 10` pass through the apertures therein and extend into the tubes 400. Sockets 401 are secured on the lower ends of the pipes 41 and these receive screw plugs 402 having orifice constrictions 403. It will be noted that certain of the pipes are coupled to downward extension pipes and that these have the sockets and plugs at their ends. The plugs of the pipes which are not extended downwards are open to a windbox 404 whilst those of the extended pipes are open to a windbox 405,

Windbox 404 is adapted to receive an oxygen supply through inlet 406 (and windbox 405 to receive a metal yhalide supply through inlet 407. It will be seen from the plan view of FIGURE 6 that the tubular passageways to the furnace for the oxygen are in groups 408 whilst those for the metal halide are in intermediate groups 409. Although a windbox supply with oriiiced plugs is shown in FIGURE 5, it will be appreciated that manifolds, and constrictions formed in orificed discs, m-ay be used instead. In fact the pattern of distribution of the respective inlet means shown in FIGURE 6 lends itself conveniently to a supply from manifolds because the latter can be straight, corresponding to the straight dispositions of the passageways for the oxygen and meta-l halide as seen in FIGURE 6. In that case the manifolds for the oxygen and metal halide may lbe supplied in opposite directions from manifolds, as indicated by the arrows.

Reverting to FIGURE 1, the top 6 of the furnace is covered by a closure 40, which is aflixed to the upper ange 9 and which surmounts a block 140 of insulating ceramic material. This closure is formed to provide a port 24 for feeding in the solid Ibed material which subsequently constitutes the bed in operation. The solid bed material is fed from a solids-feed device 71 which is shown diagrammatically in FIGURE l. 'Iihe solids-feed dev-ice consists of a ft. length of steel tube, 6 in internal di-ameter, with ya tapered bottom to which is sealed ange pipe 72, 2" in diameter, communicating with a source of compressed air. Above the taper at 73 is affixed a perforated plate, carrying holes lAe" in diameter and spaced at half-inch intervals to form a square pattern. The upper portion of the tubing is bisected over a length of 3 feet and the top of the lower portion thereof is sealed with -a horizontal steel cover 74. An inclined flanged pipe 70, 2 in diameter, leads `directly to the'furnace 1 from the lower part of the feed device at a point just below the cover. A at steel strip 75 is sealed on to the bisected length of tubing, said strip projecting downwards at 76 to about`6" from the base of the tube, measured from 73; the purpose of this projection being to prevent or minimize the veffects of `any back-flow of gases from the reactor.

There is also provided Ia port 126 in the sidewall of the furnace 1 through which the products of reaction are conveyed to ancillary apparatus for cooling and separation. The ancillary apparatus in the form which is shown in FIGURE 7 consists of a conically-shaped receiving vessel 35 into which the products discharged from the port 126 of the furnace are led through a pipe 27 havinga centrally-positioned discharge conduit 36. In this vessel, the greater part of the coarse metal oxide agglomerates settle and may be discharged, periodically or continuously according to requirement, through a Vallve 28, being aided where necessary, by vibratory motion imparted to. the sides of receiving vessel 35 by known means. The gases leaving this separator via conduit 29 are conveyed to a cyclone or, if necessary, a series of cyclones as represented by cyclone 30 wherein any of the ner agglomerates of metal oxide produced may be separated from the` gasl v lector 33 below the cyclone, and is discharged through valve 31, either periodically or continuously according to requirement. The gases after being stripped of their solid content `and usually containing chlorine as the main constituent, may be re-used directly for chlorination of metalliferous material, or they may be passed to conventional equipment for the removal of the chlorine constituent either by cooling, compression and liquefaction of the chlorine constituent or by absorption of the cooled gases in sulphur chloride or other suitable absorbent from lected for subsequent removal of thewabso-rbed chlorinecontaining gases.

Reverting to FIGURE 1, at a point towards its base, the furnace 1 is provided in the interior of the furnace with a conduit 77, which is fabricated in refractory chlorineresist-ant brick, and inclined at -an angle of about 45 to the vertical. The conduit 77 may either be sealed, or, if it is desired to introduce solid lbed material and withdraw surplus material during operation of the apparatus, the lower (and outer) end of this conduit is connected by means of `flanged joint 78 to a side arm 170 of a vertical pipe 79, 3 in internal diameter, sea-led into a flanged lid 80 of `a mild steel vessel 81, of diameter 8" land height 2 ft., the pipe 79 projecting downwards within the vessel 81 toa point approximately 3" above the topi of its tapered base. Just beneath the lower extremity of pipe 79, a stainless steel disc 82, 1/2 inch thick, is affixed to the sides of vessel S1, said disc being perforated with holes of diameter 1/16 arranged in a square pattern of side length 2". At a point approximately 6 from the sealed top, vessel 81 is provided with a pipe 83, which serves as a means of overflow. At the top of Vessel I81 is a small outlet port 84 through which the fluidizing gases clan be voided to atmosphere. Through the lower extremity of its tapered base, vessel 81 is fitted with ilanged` pipe 85, connected with a `source of compressed air. The part of the vessel 81 above the perforated disc 82 is encased in a steel jacket of conventional design 86, through which a stream of cold water can be continuously passed to cool the vessel.

A flow diagram is given in FIGURE 8 of the drawings to show how these various treatment steps may be correlated into a unitary process for zirconium dioxide or hafnium dioxide formation, it being understood that any individual treatment step diagrammatically illustrated in the flow ydiagram may be of the character illustrated above for FIGURES l to.7 or may take other forms. As illustrated, the bed material with or without pretreatment is fed continuously into the reaction zone into which the reactants are introduced. If the bed material is not fed continuously, it may be purged of accumulated metal oxide from 'time to time and replaced.

The product gases from the reaction zone entrain the rnetal oxide Iand may be cooled and then separated. The metal oxide product thus separated is purified by removal of chlorine at 51, and may then be sent to a grinding or dressing operation ands then to storage.

The ilow diagram in FIGURE 8 thus illustrates a variety of lmutually cooperating steps in processes for producing the desired oxide.

The following examples are given for the purpose of illustrating the invention; all flow rates of gas are calculated on the basis of atmospheric conditions of tempera. ture and pressure.

Example I V-aporized zirconium tetrachloride was reacted with oxygen in a reactor of the character of that shown in l FIGURE 1 comprising a vertical steel shaft furnace in which was a fluid bed of particulate Zircon with a mean particle size of g.

The bed, of 24 inch diameter, was initially iluidized to la lluidized height of 24 inches by air preheated to 400 C. and introduced into the bed through the passages 212,

312 and 112. The bed was heated by a gas poker to ll C. inserted into the reactor through the solids feed port 24, the poker then being withdrawn and the port 24 sealed. With the reactor and bed lthus prepared, the air streams through the passages 212 and 312 were replaced by streams of oxygen iiowing at 22.5 cubic feet per minute, measured at 20 C. and atmospheric pressure, the entering oxygen, however, being preheated to 200 C. to avoid cooling the hearth unit excessively.

Zirconium tetrachloride vapor was generated by feeding solid ZrCl.,i of less than mesh B.S.S. to an auxiliary fluidized bed vaporizer of 9 inches diameter containing a 12 inch deep bed of particulate zircon having an average size of' 14S/r, fluidized by the passage of 3 cubic feet per minute of dry nitrogen measured at 20 C. and atmospheric pressure. 'l'he auxiliary bed temperature was maintained in the range 390 C.-4l0 C. by indirect heating.

Y After discontinuing the preliminary air ilow through the passages 112 f the main reactor and following a nitrogen sweep Vof thesepassages, the ZrCl4 vapor and nitrogen mixture issuing from the vaporizer was conducted to the reactor hearth at 9 lbs./ min. in electrically heated lines to maintain a vapor temperature in excess of 370 C. when entering the bed through the passages 112. The depth of the lbed was low enough so that the pressure drop across the conduits 1'12, 212 and 312 was in excess of one-half the pressure drop across the iluidized bed.

A feed of zircon with a mean particle size of 145g was supplied to the bed in the main reactor, by means of the feed arrangement 71, at a rateof 90-140 lbs./hour, to control the bed size and maintain reaction temperature in the range l040-l060 C. Excess bed material was removed through the overow device 79. Because of the accretionofZrOZ on the bed (equivalent to 21% the ZrCl4 feed), the removed bed material was crushed after cooling toY provide the desired size range required to be fed back to the reactor. Operating in this manner, the run was continued for 72 hours,.until voluntary shut down. The zirconia product was entrained in the effluent gas mixture of chlorine, oxygen and nitrogen, the whole being cooled by conventional means, prior-,to separation of the solids.

After neutralization, the product was found to be substantially in the monoclinic form with a specic surface area of l2 square metres per gram. It was very uniform with a mean weight particle size of 0.l5/.t.

Example 1I Hafnium tetrachloride lis ,prepared by chlorinating a pelleted mixture of 20 gms. HfO2 and 2 gms. carbon at 1000 C., using a chlorine rate of 500 cc./min. The resultant stream of HfCli and carbon gases is passed directly at a temperature of 500 C. into the base of a vertical silica reactor tube, 24 inches high and 1 inch in diameter. This tube contains a bed of 60-100 mesh B.S.S. silica sand havi-ng a depth of 5 inches when static. Thereactor tube is maintained at 1050D C. Oxygen metered at 500 cc./min. is also passed into the base of thereactor through a separate injector. The gases injected into the base of the reactor fluidize the bed of sand contained therein.

` The effluent gases from the top of the reactor tube are passed through a glass ask where solids entrained therein .aredeposited n These conditions are maintained for 7 minutes before thel eiciency of chlorination of the HOZ falls below 90%, when the process is halted. Throughout the period 12 1 as limitations upon the scope of the claims except insofar as they are included in the' accompanying claims.

We claim:

l. In a method of preparing metal oxide by establishing `a uidized bed of solids and introducing a halide of a metal of the group consisting of zirconium and hafnium which is in vapor state at 350" C. and oxygen into the bed and carrying away at least a portion of the metal oxide with the gases leaving the bed, the improvement which comprises introducing the metal halide into a lower portion of the bed in a multiplicity of dispersed streams and introducing the oxygen into a lower portion of the bed in a multiplicity of other dispersed streams which are interspersed with the ldispersed metal halide streams, the streams entering the bed around the perimeter thereof being streams of oxygen, and maintaining the depth of the bed low enough so that the pressure drop across the conduits is at least one-half the pressure drop across the bed and the ascending streams of metal halide co-mingle intimately with the ascending streams of oxygen in the bed within the perimeter thereof.

2. A process for producing oxides which comprises passing upwardly through a uidized bed of inert solid particles a multiplicity of streams of a gas comprising elemental oxygen and a multiplicity of streams consisting essentiaily of a vaporized halide of an element of the group consisting of zirconium and hafnium, maintaining the depth of said bed low enough so that the pressure drop of the streams as they pass into the bed is at least onehalf the pressure drop across the bed, and maintaining the' temperature of the bed at which oxygen reacts with the halide; said multiplicity of oxygen streams and said multiplicity of halide streams being mutually interspersed to ensure intermingling thereof in the bed from substantially immediately adjacent the bed bottom upwardly through the bed, the combined force of the streams substantially uniformly iiuidizing the bed.

3. A process for producing oxides which comprises passing upwardly through a i'luidized bed of inert solid particles a multiplicity of streams of a gas comprising elemental oxygen and a multiplicity of streams of a Vaporizedy halide of an element of the group consisting of zirconium and hafnium, maintaining the depth of said bed low enoughr so that the pressure `drop of the streams as they pass into the bed is at least one-half the pressure drop across the bed, and maintaining the temperature of the bed at which the Vhalide reacts with oxygen; said multiplicity of oxygen streams and s aid multiplicity of halide streams being mutually interspersed .to ensure intermingling thereof in the bed from substantially immediately adjacent the bed bottom upwardly through the bed, wherein the combined force of the streams substantially uniformly uidizes the bed, the ystreams nearest the periphery of the bed being oxygen streams.

4. In a method of preparing a metal oxide in -a iluid-l ized bed comprising inert particles by introduction of a halide of a metal of the group consisting of zirconium of operation a white `solid product is collected in the glass ask fitted to the top of the reactor and, on examination,

and hafnitun, and oxygen into the bedmaintained at an elevated temperature at which oxygen reacts with said halide, the steps of externally heat insulating said bed, maintaining the bed of such capacity as to retain suli`1- cientheat vfor the temperature to be substantially autothermally maintained, and maintaining the depth of said bed low `enough lso that 'said halide and oxygen undergo a pressure drop, on being introduced into 4the bed, at least one-half the pressure drop acrossthe bed.

5. The method according'to claim 4 wherein the bed is cylindrical and of a diameter of theiorder of at least yized halideof a metal of the group consisting of zirconium and hafnium with said first and second streams being interspersed with each other to ensure intermingling within the bed, forcing the streams upwardly into the bed at such velocities that their combined force uniformly fluidizes the bed, maintaining the depth of the bed low enough so that said streams undergo a pressure drop on being passed into the bed, at least one-half the pressure drop across the bed, and maintaining the bed of such cross Section and so insulating the bed against escape of heat as to enable the reaction to continue autothermally.

7. In a method of preparing zirconium dioxide by establishing a fluid bed of solids andintroducing zirconium tetrachloride and oxygen into the bed and carrying at least a portion of the zirconium dioxide away with the gases leaving the uidized bed, the improvement which comprises introducing `the oxygen into a lower portion of the bed through a plurality of conduits from a common source and maintaining the depth of the bed low enough so that `the pressure drop across the conduits is at least one-half the pressure drop across the bed.

8. In the method of preparing zirconium dioxide by establishing a iluid bed of solids and introducing zirconium tetrachloride Iand oxygen into the bed and carrying at least a portion of the zirconium dioxide away with the gases leaving the iluidized bed, the improvement which comprises introducing the oxygen and the zirconium tetrachloride into a lower portion of the bed through a plurality of conduits from a common source and maintaining the depth of the bed low enough so that the pressure drop across the conduits is at lea-st one-half the pressure drop across the bed.

9. The process of claim 8 wherein the depth of the bed is not in excess of 2.5 feet.

l0. The process of claim 8 wherein the depth of the bed is not in .excess of 2.5 feet and the diameter of the bed is in excess of 1.5 feet.

11. In the method of preparing zirconium dioxide by establishing a iluid bed of solids, introducing zirconium tetrahalide and oxygen into the bed and carrying at least a portion of the zicronium dioxide away with the gases leaving the uidized bed, the improvement which cornprises introducing the tetrahalide into a lower portion of the bed through a plurality of conduits from a commonv source and maintaining the depth of the bed low enough so that the pressure drop across the conduits is at least one-half the pressure drop -across the bed.

12. In the method of preparing zirconium dioxide by establishing a fluid bed of solids and introducing zirconium tetrachloride and oxygen into the bed and carrying at least a portion of the zirconium dioxide away with the gases r leaving the uidized bed, the improvement which comprises introducing the tetrachloride into a lower portion of the bed through la plurality of conduits from a common ysource and maintaining the depth of the bed low enough so that the pressure drop across the conduits is at least one-half the pressure drop across the bed.

13. In the method of preparing zirconium dioxide by establishing a iiuid bed of solids, introducing zirconium tetrahalide and oxygen into the bed, and carrying at least a portion of the zirconium dioxide away with the gases leaving the iluidized bed, the improvement which comprises introducing a member of the group consisting of zirconium tetrahalide, oxygen, and a mixture of zirconium tetrahalide and oxygen, into a lower portion of the bed through a plurality of conduits from a common source of said member, and maintaining the depth of the bed low enough so that the pressure drop across the conduits approximates the pressure drop across the bed.

14. In the method of preparing a metal oxide by establishing a fluid bed of solids and introducing oxygen and a chloride of a metal of the group consisting of zirconium and hafnium into the bed and carrying at least a portion of the metal oxide away with the gases leaving the uidized bed, the improvement which comprises introducing the oxygen and the chloride into a lower portion of the bed through a plurality of conduits from a common source and maintaining the depth of the bed low enough so that the pressure drop across the conduits is at least one-half the pressure drop across the bed.

l5. In the method of preparing a metal oxide by establishing a tiuid bed of solids, introducing oxygen and a halide of a metal of the group consisting of zirconium and hafnium into the bed, and carrying at least a portion of the metal oxide away with the gases leaving the huidized bed, the improvement which comprises introducing into a lower portion of the bed through a plurality of conduits from a common source a member of the group consisting of a halide, oxygen, and a mixture of the halide and oxygen, said halide being a halide of a metal of the group consisting of zirconium and hafnium, and maintaining the depth of the bed low enough so that the pressure drop across the conduits approximates the pressure drop across the bed.

16. The method of claim 15 in which the halide is a zirconium halide.

17. The method of claim 15 in which the halide is a hafnium halide.

References Cited in the file of this patent UNITED STATES PATENTS 468,216 Birge Feb. 2, 1892 2,028,326 Hanks et al. Ian. 12, 1936 2,468,508 Munday Apr. 26, 1949 2,622,969 Deanesly et al. Dec. 23, 1952 2,676,998 Kuntz et al. Apr. 27, 1954 2,701,179 McKinney Feb. 1, 1955 2,760,846 Richmond et al. Aug. 28, 1956 2,791,490 Wilcox May 7, 1957 2,828,187 Evans et al. Mar. 25, 1958 2,841,476 Dalton July 1, 1958 2,855,273 Evans et al Oct. 7, 1958 FOREIGN PATENTS 661,685 Great Britain Nov. 28, 1951 

1. IN A METHOD OF PREPARING METAL OXIDE BY ESTABLISHING A FLUIDIZED BED OF SOLIDS AND INTRODUCING A HALIDE OF A METAL OF THE GROUP CONSISTING OF ZIRCONIUM AND HAFNIUM WHICH IS IN VAPOR STATE AT 350*C. AND OXYGEN INTO THE BED AND CARRYING AWAY AT LEAST A PORTION OF THE METAL OXIDE WITH THE GASES LEAVING THE BED, THE IMPROVEMENT WHICH COMPRISES INTRODUCING THE METAL HALIDE INTO A LOWER PORTION OF THE BED IN A MULTIPLICITY OF DISPERSED STREAMS AND INTRODUCING THE OXYGEN INTO A LOWER PORTION OF THE BED IN A MULTIPLICITY OF OTHER DISPERSED STREAMS WHICH ARE INTERSPERSED WITH THE DISPERSED METAL HALIDE STREAMS, THE STREAMS ENTERING THE BED AROUND THE PERIMETER THEREOF BEING STREAMS OF OXYGEN, AND MAINTAINGING THE DEPTH OF THE BED LOW ENOUGH SO THAT THE PRESSURE DROP ACROSS THE CONDUITS IS AT LEAST ONE-HALF THE PRESSURE DROP ACROSS THE BED AND THE ASCENDING STREAMS OF METAL HALIDE CO-MINGLE INTIMATELY WITH THE ASCENDING STREAMS OF OXYGEN IN THE BED WITHIN THE PERIMETER THEREOF. 